EP0705797A2 - Articles fabriqués en oxyde de silicone et/ou autres oxydes métaliques mixtes et procédé de leur préparation en leur dimensions "finales" ou "presque finales" - Google Patents

Articles fabriqués en oxyde de silicone et/ou autres oxydes métaliques mixtes et procédé de leur préparation en leur dimensions "finales" ou "presque finales" Download PDF

Info

Publication number: EP0705797A2
Authority: EP; European Patent Office
Prior art keywords: final; optical; dimensions; silicon oxide; tolerance
Prior art date: 1994-10-06
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Granted

Application number

EP95114722A

Other languages

German (de)

English (en)

Other versions

EP0705797B1 (fr

EP0705797A3 (fr

Inventor

Lorenzo Costa

Paolo Chiurlo

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Enichem SpA

Original Assignee

Enichem SpA

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1994-10-06

Filing date

1995-09-19

Publication date

1996-04-10

1995-09-19 Application filed by Enichem SpA filed Critical Enichem SpA

1996-04-10 Publication of EP0705797A2 publication Critical patent/EP0705797A2/fr

1996-08-21 Publication of EP0705797A3 publication Critical patent/EP0705797A3/fr

2000-03-29 Application granted granted Critical

2000-03-29 Publication of EP0705797B1 publication Critical patent/EP0705797B1/fr

2015-09-19 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 27
229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 11
238000000034 method Methods 0.000 title abstract description 24
229910044991 metal oxide Inorganic materials 0.000 title abstract description 4
238000002360 preparation method Methods 0.000 title description 6
230000003287 optical effect Effects 0.000 claims abstract description 42
230000003746 surface roughness Effects 0.000 claims abstract description 10
238000001429 visible spectrum Methods 0.000 claims abstract description 7
238000002211 ultraviolet spectrum Methods 0.000 claims abstract description 6
239000000919 ceramic Substances 0.000 claims abstract 2
230000000737 periodic effect Effects 0.000 claims description 3
GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 2
YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims 2
PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims 2
OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 2
239000004964 aerogel Substances 0.000 abstract description 26
239000000463 material Substances 0.000 abstract description 19
238000000465 moulding Methods 0.000 abstract description 7
238000003980 solgel method Methods 0.000 abstract description 2
238000007669 thermal treatment Methods 0.000 abstract description 2
239000000047 product Substances 0.000 description 22
239000000499 gel Substances 0.000 description 11
239000005304 optical glass Substances 0.000 description 6
239000000377 silicon dioxide Substances 0.000 description 4
BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
238000004458 analytical method Methods 0.000 description 3
238000010586 diagram Methods 0.000 description 3
238000005516 engineering process Methods 0.000 description 3
239000011521 glass Substances 0.000 description 3
238000004519 manufacturing process Methods 0.000 description 3
229920003023 plastic Polymers 0.000 description 3
239000004033 plastic Substances 0.000 description 3
230000035945 sensitivity Effects 0.000 description 3
235000012239 silicon dioxide Nutrition 0.000 description 3
238000003756 stirring Methods 0.000 description 3
238000000352 supercritical drying Methods 0.000 description 3
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
239000012707 chemical precursor Substances 0.000 description 2
238000001246 colloidal dispersion Methods 0.000 description 2
238000001816 cooling Methods 0.000 description 2
239000010432 diamond Substances 0.000 description 2
229910003460 diamond Inorganic materials 0.000 description 2
238000011049 filling Methods 0.000 description 2
238000001879 gelation Methods 0.000 description 2
239000001307 helium Substances 0.000 description 2
229910052734 helium Inorganic materials 0.000 description 2
SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
230000007062 hydrolysis Effects 0.000 description 2
238000006460 hydrolysis reaction Methods 0.000 description 2
239000000543 intermediate Substances 0.000 description 2
239000007788 liquid Substances 0.000 description 2
238000002844 melting Methods 0.000 description 2
230000008018 melting Effects 0.000 description 2
238000006068 polycondensation reaction Methods 0.000 description 2
239000010453 quartz Substances 0.000 description 2
229910052710 silicon Inorganic materials 0.000 description 2
239000010703 silicon Substances 0.000 description 2
-1 silicon alkoxide Chemical class 0.000 description 2
238000001228 spectrum Methods 0.000 description 2
VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
229910002020 Aerosil® OX 50 Inorganic materials 0.000 description 1
VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
239000004965 Silica aerogel Substances 0.000 description 1
239000004411 aluminium Substances 0.000 description 1
XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
229910052782 aluminium Inorganic materials 0.000 description 1
239000000908 ammonium hydroxide Substances 0.000 description 1
230000015572 biosynthetic process Effects 0.000 description 1
238000001354 calcination Methods 0.000 description 1
229910052799 carbon Inorganic materials 0.000 description 1
238000005119 centrifugation Methods 0.000 description 1
239000007795 chemical reaction product Substances 0.000 description 1
239000000460 chlorine Substances 0.000 description 1
229910052801 chlorine Inorganic materials 0.000 description 1
239000008119 colloidal silica Substances 0.000 description 1
238000007796 conventional method Methods 0.000 description 1
239000010949 copper Substances 0.000 description 1
229910052802 copper Inorganic materials 0.000 description 1
238000000280 densification Methods 0.000 description 1
230000006866 deterioration Effects 0.000 description 1
239000006185 dispersion Substances 0.000 description 1
238000001035 drying Methods 0.000 description 1
238000002474 experimental method Methods 0.000 description 1
230000002349 favourable effect Effects 0.000 description 1
238000000227 grinding Methods 0.000 description 1
238000010438 heat treatment Methods 0.000 description 1
239000007970 homogeneous dispersion Substances 0.000 description 1
239000012456 homogeneous solution Substances 0.000 description 1
230000002706 hydrostatic effect Effects 0.000 description 1
238000002329 infrared spectrum Methods 0.000 description 1
239000000203 mixture Substances 0.000 description 1
230000003647 oxidation Effects 0.000 description 1
238000007254 oxidation reaction Methods 0.000 description 1
230000001590 oxidative effect Effects 0.000 description 1
238000005498 polishing Methods 0.000 description 1
229920000728 polyester Polymers 0.000 description 1
239000000843 powder Substances 0.000 description 1
239000005049 silicon tetrachloride Substances 0.000 description 1
239000007790 solid phase Substances 0.000 description 1
239000002904 solvent Substances 0.000 description 1
239000000126 substance Substances 0.000 description 1
238000003786 synthesis reaction Methods 0.000 description 1
230000009466 transformation Effects 0.000 description 1
238000000844 transformation Methods 0.000 description 1
238000002604 ultrasonography Methods 0.000 description 1

Images

Classifications

- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/12—Other methods of shaping glass by liquid-phase reaction processes
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/31—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with germanium
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B2201/00—Type of glass produced
- C03B2201/06—Doped silica-based glasses
- C03B2201/30—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi
- C03B2201/40—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn
- C03B2201/42—Doped silica-based glasses doped with metals, e.g. Ga, Sn, Sb, Pb or Bi doped with transition metals other than rare earth metals, e.g. Zr, Nb, Ta or Zn doped with titanium

Definitions

the present invention relates to optical components in silicon oxide and/or other mixed metallic oxides having dimensional precision which has surface roughness tolerance and profilometric accuracy within the specifications described for visible and ultraviolet spectrum ranges.
the above manufactured articles have "final” or “almost final” dimensions as they are obtained by the isotropic dimensional reduction (miniaturization) of amorphous monolithic materials, called aerogels, in turn prepared by means of cold moulding techniques based on sol-gel processes.
optical materials and in particular transparent optical materials such as silica or molten quartz and optical glass, owing to their hardness and fragility, are difficult to process as the direct hot moulding of these optical components and devices is generally not possible for reasons of product quality.
the optical products obtained from plastic materials do not have an acceptable quality as the material cannot be accurately processes owing to the fact that it is too soft.
optical components with definite dimensions can be obtained by suitably treating a gel deriving from the hydrolysis of a silicon alkoxide.
U.S. patent 4.680.049 describes a method for the preparation of optical glass based on silicon oxide which involves an initial hydrolysis of a silicon alkoxide, the drying of the above gel and a final thermal syntherization treatment until an optical glass with definite dimensions is obtained.
the two diagrams shown in the above figure represent the configuration of the upper surface of the aerogel (diagram A) and the corresponding surface of the densified product (diagram B) respectively.
the invention relates to the preparation of the above products, according to a process which involves the accurate geometrical definition of the aerogel by:
moulds having much greater dimensions than the manufactured article, have an internal volume which is defined as a "homothetic copy” of the "end"-product itself, which is characterized in terms of profilometric accuracy, surface roughness and scaling ratio with the product itself.
the product thus obtained has "almost final” dimensions i.e. it requires only an optical polishing with the conventional methods or, at the best, it has “final” dimensions i.e. it does not require any conventional optical processing.
the overall result of the present invention is therefore the economical production of optical components and devices made of silica glass or other optical glass using a new cold moulding technique based on specific sol-gel synthesis processes.
the present invention consequently relates to optical articles, components or devices, with "final” or “almost final” dimensions and completely isotropic, consisting of silicon oxide, either alone or in the presence of one or more oxides belonging to groups III° to VI° of the Periodic Table, and exceptionally also other groups, said optical articles, components or devices having dimensional precision which has tolerance to surface roughness and profilometric accuracy required for the visible and ultraviolet spectrum ranges, characterized in that said tolerance being between 1/2 and 1/10 wave length corresponding to the range 0.350-0.02 micrometers and, preferably, equal to 1/4 wave length corresponding on an average, in the visible range, to 0.275 micrometers.
TEOS tetraethylorthosilicate
colloidal silica powder (Aerosil OX50 - Degussa) prepared from silicon tetrachloride by oxidation at high temperatures, is added, still under vigorous stirring, to this solution.
the mixture obtained is homogenized using ultra-sounds for a duration of about ten minutes and then clarified by centrifugation.
the homogeneous dispersion obtained is poured into cylindrical containers of polyester with a diameter of 5.0 cm and height of 2.0 cm, which are hermetically closed, placed in an oven and maintained at 50°C for 12 hours.
the gel which is obtained is suitably washed with ethanol and subsequently supercritically dried in an autoclave at a temperature of 300°C or in any case higher than the critical temperature of the solvent.
An aerogel is obtained which is calcinated at a temperature of 800°C in an oxidizing atmosphere.
the dimensions of the aerogel obtained are those of the internal volume of the initial cylindrical container.
the disk of silica aerogel after calcination, is subjected to a stream of helium containing 2% of chlorine, at a temperature of 800°C and for a duration of 30 minutes to remove the silanolic groups present; the aerogel disk is finally heated in a helium atmosphere to a temperature of 1400°C for the duration of one hour so that the silica reaches complete densification and consequent miniaturization.
the disk After cooling, the disk reaches the desired final dimensions (diameter 2.5 cm and height 1.0 cm), maintaining a homothetic ratio with the form of the initial aerogel determined by the initial mould.
Moulds are prepared with an internal surface finished with optical specifications (surface roughness less than 1/5 with a wave length corresponding to less than 0.08 micrometers).
the internal volume of the moulds corresponds to a cylinder of 5.0 cm in diameter and 2.0 cm in height.
One of the bases of the cylinder consists of the optical surface to be duplicated.
the moulds thus filled are hermetically closed, placed in an oven and maintained at 20°C for 12 hours.
the profilometric and surface roughness results measured on the optical surface of the aerogel, have the same optical quality as the original surface with a roughness of less than 0.1 micrometres, corresponding to 1/5 average wave length of the visible spectrum range.
the constants for the densified product having a diameter of 15 mm ⁇ 0.05 and height of 6.25 mm ⁇ 0.10, are the following:
a silicic sol was prepared with the procedure of example 2.
a series of 3 aerogels was prepared using the above mould according to the procedures described in example 2.
each aerogel was placed in line at the centre of a Mitutoyo series 332 profile projector and compared to the theoretical profile corresponding to the equation of the aspherical profile.
the comparison was carried out by direct placement over the screen.
each analysis was carried out with photographic aid and subsequent projection on a huge screen providing a sensitivity of up to a ten thousandth of the dimension of the object.
the aerogels were then densified (miniaturized), with the thermal treatment described in example 1 and compared with the respective theoretical profile as in the case of the aerogels.
the maximum deviation, relating to the respective theoretical profiles is less than 0.002 mm, a value which is considered as the limit of the sensitivity of the method.
FIG. 2 An example of profilometric determination is shown in Figure 2 wherein the aspherical profile of the aerogel is comparable to the theoretical profile generated by the equation (see the dark external line) and the site of the theoretical profile points has been slightly moved towards the outside to facilitate observation of the trend parallel to the surface.

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Chemical & Material Sciences (AREA)
Engineering & Computer Science (AREA)
Chemical Kinetics & Catalysis (AREA)
Manufacturing & Machinery (AREA)
Materials Engineering (AREA)
Organic Chemistry (AREA)
Glass Compositions (AREA)
Silicon Compounds (AREA)
Compositions Of Oxide Ceramics (AREA)
Glass Melting And Manufacturing (AREA)
Oxygen, Ozone, And Oxides In General (AREA)

EP95114722A 1994-10-06 1995-09-19 Procédé de fabrication d'articles optiques en oxyde de silicone et/ou autres oxydes métalliques mixtes en leur dimensions "finales" ou "presque finales" Expired - Lifetime EP0705797B1 (fr)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
ITMI942035		1994-10-06
ITMI942035A IT1270628B (it)	1994-10-06	1994-10-06	Manufatti in ossido di silicio e/o altri ossidi metallici misti e procedimento per la loro preparazione in dimensioni finali o quasi finali

Publications (3)

Publication Number	Publication Date
EP0705797A2 true EP0705797A2 (fr)	1996-04-10
EP0705797A3 EP0705797A3 (fr)	1996-08-21
EP0705797B1 EP0705797B1 (fr)	2000-03-29

Family

ID=11369657

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP95114722A Expired - Lifetime EP0705797B1 (fr)	1994-10-06	1995-09-19	Procédé de fabrication d'articles optiques en oxyde de silicone et/ou autres oxydes métalliques mixtes en leur dimensions "finales" ou "presque finales"

Country Status (10)

Country	Link
US (2)	US6567210B2 (fr)
EP (1)	EP0705797B1 (fr)
JP (1)	JPH08190001A (fr)
AT (1)	ATE191207T1 (fr)
CA (1)	CA2159975C (fr)
DE (1)	DE69515953T2 (fr)
DK (1)	DK0705797T3 (fr)
ES (1)	ES2143572T3 (fr)
GR (1)	GR3033159T3 (fr)
IT (1)	IT1270628B (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US6699808B1 (en)	1999-09-09	2004-03-02	Wacker-Chemie Gmbh	High-solids SiO2 dispersions, process for producing them, and their use
WO2004083137A1 (fr)	2003-03-20	2004-09-30	Degussa Novara Technology S.P.A.	Articles optiques, leur procede de preparation et moyens appropries
DE10339676A1 (de) *	2003-08-28	2005-03-24	Wacker-Chemie Gmbh	SiO2-Formkörper, Verfahren zu ihrer Herstellung und Verwendung
US6890873B2 (en)	2000-08-21	2005-05-10	Degussa Ag	Glass prepared from pyrogenically prepared silicon dioxide
WO2005123578A1 (fr) *	2004-06-22	2005-12-29	Degussa Ag	Sol d'oxyde metallique, couche ainsi obtenue et article ainsi forme
EP1700830A1 (fr)	2005-03-09	2006-09-13	Novara Technology S.R.L.	Procédé pour la production des monoliths au moyen du procédé sol-gel
KR100855809B1 (ko) *	2004-06-22	2008-09-01	에보니크 데구사 게엠베하	금속 산화물 졸, 이를 사용하여 생성된 층 및 성형품

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE10158521B4 (de) *	2001-11-29	2005-06-02	Wacker-Chemie Gmbh	In Teilbereichen oder vollständig verglaster SiO2-Formkörper und Verfahren zu seiner Herstellung
DE10260320B4 (de) *	2002-12-20	2006-03-30	Wacker Chemie Ag	Verglaster SiO2-Formkörper, Verfahren zu seiner Herstellung und Vorrichtung
US8455165B2 (en) *	2006-09-15	2013-06-04	Cabot Corporation	Cyclic-treated metal oxide
US20080070146A1 (en)	2006-09-15	2008-03-20	Cabot Corporation	Hydrophobic-treated metal oxide
US8435474B2 (en) *	2006-09-15	2013-05-07	Cabot Corporation	Surface-treated metal oxide particles
JP2011100111A (ja) *	2009-10-09	2011-05-19	Seiko Epson Corp	光学物品、光学物品の製造方法、電子機器
CN106154359B (zh) *	2015-03-24	2018-03-20	福州高意光学有限公司	一种非球面光学元件制作方法
JP2018090440A (ja) *	2016-12-02	2018-06-14	クアーズテック株式会社	鋭角部を有する光学部品の製造方法

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Publication number	Priority date	Publication date	Assignee	Title
US4680049A (en)	1986-08-15	1987-07-14	Gte Laboratories Incorporated	Process for molding optical components of silicate glass to a near net shape optical precision
US5207814A (en)	1989-02-10	1993-05-04	Enichem S.P.A.	Process for preparing monoliths of aerogels of metal oxides
US5297814A (en)	1992-11-20	1994-03-29	Peters Eddie R	Clipboard for teaching children to write correctly

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FR2507171A1 (fr) *	1981-06-04	1982-12-10	Zarzycki Jerzy	Aerogels de silice monolithiques, leur preparation et leur utilisation pour la preparation d'articles en verre de silice et de materiaux thermiquement isolants
CA1204209A (fr) *	1981-10-27	1986-05-06	Hisao Kinjo	Support d'enregistrement pour appareil d'enregistrement et de lecture
US4776867A (en) *	1986-08-15	1988-10-11	Gte Laboratories Incorporated	Process for molding optical components of silicate glass to a near net shape optical precision
JPS6486344A (en) *	1987-09-29	1989-03-31	Victor Company Of Japan	Information recording carrier and production thereof
US5069816A (en) *	1988-01-11	1991-12-03	Mmii Incorporated	Zirconium silica hydrogel compositions and methods of preparation
JPH02120246A (ja) *	1988-10-27	1990-05-08	Seiko Epson Corp	微細パターン転写ガラスの製造方法
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EP0535388A1 (fr) *	1991-09-03	1993-04-07	Konica Corporation	Préforme et élément optique en verre et procédés de leur fabrication
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IT1256359B (it) *	1992-09-01	1995-12-01	Enichem Spa	Procedimento per la preparazione di componenti e dispositivi ottici indimensioni finali o quasi finali, e prodotti cosi' ottenuti

1994
- 1994-10-06 IT ITMI942035A patent/IT1270628B/it active IP Right Grant
1995
- 1995-09-19 DK DK95114722T patent/DK0705797T3/da active
- 1995-09-19 ES ES95114722T patent/ES2143572T3/es not_active Expired - Lifetime
- 1995-09-19 AT AT95114722T patent/ATE191207T1/de not_active IP Right Cessation
- 1995-09-19 EP EP95114722A patent/EP0705797B1/fr not_active Expired - Lifetime
- 1995-09-19 DE DE69515953T patent/DE69515953T2/de not_active Expired - Lifetime
- 1995-09-25 US US08/533,551 patent/US6567210B2/en not_active Expired - Fee Related
- 1995-10-05 CA CA002159975A patent/CA2159975C/fr not_active Expired - Fee Related
- 1995-10-06 JP JP7260528A patent/JPH08190001A/ja active Pending
2000
- 2000-04-04 GR GR20000400852T patent/GR3033159T3/el not_active IP Right Cessation
- 2000-08-30 US US09/651,109 patent/US6374637B1/en not_active Expired - Fee Related

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4680049A (en)	1986-08-15	1987-07-14	Gte Laboratories Incorporated	Process for molding optical components of silicate glass to a near net shape optical precision
US5207814A (en)	1989-02-10	1993-05-04	Enichem S.P.A.	Process for preparing monoliths of aerogels of metal oxides
US5297814A (en)	1992-11-20	1994-03-29	Peters Eddie R	Clipboard for teaching children to write correctly

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US6699808B1 (en)	1999-09-09	2004-03-02	Wacker-Chemie Gmbh	High-solids SiO2 dispersions, process for producing them, and their use
US6890873B2 (en)	2000-08-21	2005-05-10	Degussa Ag	Glass prepared from pyrogenically prepared silicon dioxide
WO2004083137A1 (fr)	2003-03-20	2004-09-30	Degussa Novara Technology S.P.A.	Articles optiques, leur procede de preparation et moyens appropries
KR100755736B1 (ko) *	2003-03-20	2007-09-06	데구사 노바라 테크놀로지 에스.피.에이.	광학 제품 및 이를 제조하기 위한 졸-겔법
AU2004222140B2 (en) *	2003-03-20	2009-11-05	Evonik Degussa Gmbh	Optical articles and sol-gel process for their manufacture
US8029887B2 (en)	2003-03-20	2011-10-04	Evonik Degussa Gmbh	Optical articles and sol-gel process for their manufacture
DE10339676A1 (de) *	2003-08-28	2005-03-24	Wacker-Chemie Gmbh	SiO2-Formkörper, Verfahren zu ihrer Herstellung und Verwendung
WO2005123578A1 (fr) *	2004-06-22	2005-12-29	Degussa Ag	Sol d'oxyde metallique, couche ainsi obtenue et article ainsi forme
KR100855809B1 (ko) *	2004-06-22	2008-09-01	에보니크 데구사 게엠베하	금속 산화물 졸, 이를 사용하여 생성된 층 및 성형품
EP1700830A1 (fr)	2005-03-09	2006-09-13	Novara Technology S.R.L.	Procédé pour la production des monoliths au moyen du procédé sol-gel

Also Published As

Publication number	Publication date
CA2159975A1 (fr)	1996-04-07
CA2159975C (fr)	2006-07-11
DE69515953D1 (de)	2000-05-04
GR3033159T3 (en)	2000-08-31
EP0705797B1 (fr)	2000-03-29
ITMI942035A0 (it)	1994-10-06
IT1270628B (it)	1997-05-07
JPH08190001A (ja)	1996-07-23
ATE191207T1 (de)	2000-04-15
ES2143572T3 (es)	2000-05-16
US6374637B1 (en)	2002-04-23
US6567210B2 (en)	2003-05-20
DK0705797T3 (da)	2000-07-24
ITMI942035A1 (it)	1996-04-06
EP0705797A3 (fr)	1996-08-21
US20020063953A1 (en)	2002-05-30
DE69515953T2 (de)	2000-10-05

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